Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Syntheses:
Trichlorostannane.
Anhydrous SnCl
2
(20 g) and 70 mL of absolute ether were placed in a three-necked flask, fitted with a condenser, gas bubbler and septum, which had been previously flushed with dry nitrogen for ~5 minutes. The flask was immersed in a waterbath at room temperature and dry hydrogen chloride was passed through the suspension for ~2 hours to yield an oily layer of HSnCl
3
•2(C
2
H
5
)
2
O, which is insoluble in ether.
The upper layer was removed with a syringe through the septum and the lower layer of the etherate complex was used for subsequent reaction.
Trichlorogermane.
Germanium tetrachloride (8.0 mL, 0.069 mol) was dissolved in 40 mL of absolute ether in a round bottom two-necked flask, equipped with a reflux condenser and a septum inlet, which had been previously flushed with dry nitrogen. A mineral oil bubbler was used in order to keep air out of the reaction flask.
Tetramethyldisiloxane (12.0 mL, 0.069 mol) was added and the homogenous solution was stirred at room temperature for ~4-5 hours. (In order to speed up the reaction the reaction vessel can be immersed in a water-bath at ~40° C). After completion, the reaction mixture separated into two layers. The upper layer (excess ether) was removed by means of a syringe through the septum and the lower greenish-yellow oily layer

Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004 containing the etherate complex HGeCl
3
•2(C
2
H
5
)
2
O was used immediately for further reaction
Cl
3
Sn(CH
2
)
2
COOH . SnCl
2
(20.0 g, 0.105 mol) was stirred in ~100 mL absolute ether and 7.2 mL (0.105 mol) acrylic acid was added at once. The reaction flask was immersed in an ice-water bath and was flushed with dry nitrogen for ~3 minutes. Hydrogen chloride was slowly bubbled into the reaction mixture, causing an exothermic reaction. After ~30 minutes all the tin (II) chloride had dissolved and the 1 H NMR of the crude mixture showed no unreacted acrylic acid.
The excess ether and HCl were removed under vacuum in a rotary evaporator and the remaining amorphous off-white powder was was purified by several washings with chloroform and air dried. Yield: 19.9 g (64%). NMR(D
2
O):
1
H; 0.99(t), 1.92(t) ;
2
J
H-Sn
=
198Hz, 3 J
H-Sn
= 128Hz. 13 C; 28.9, 29.2, 182.6, 1 J
C-Sn
= 1090Hz. 119 Sn{ 1 H}; -34.1.
The dramatic chemical shift difference between the ester and acid derivatives is attributed to zwitterion formation via dehydrochlorination of the acid in aqueous solution,
Cl
3
SnCH
2
CH
2
COOH

Cl
2
Sn
+
CH
2
CH
2
COO
-
+ HCl
(R.E. Hutton and J.W. Burley, J. Organometal. Chem.
, 1978, 156 , 369)
Cl
3
Sn(CH
2
)
2
CN Acrylonitrile (5.2 mL, 0.079 mol) was added dropwise to 0.053 mol of
HSnCl
3
•2C
2
H
5
O complex. The reaction mixture was stirred in a water bath at ~60° C for two hours. By the end of this time period the solution had turned yellow. The excess acrylonitrile, ether, and HCl were removed in a rotary evaporator and the yellow pasty residue obtained was washed twice with 30 mL chloroform. The product dissolved exothermically in DMF, yielding a dark orange-brown solution. This solution, with an

Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004 estimated concentration 1.2 mmol/mL Cl
3
Sn(CH
2
)
2
CN, was used for further reactions.
Yield: 9.1 g (61%). NMR (DMF): 1 H; 1.08(t), 2.08(t).
Cl
3
Ge(CH
2
)
2
COOCH
3
Methyl acrylate (5.0 mL, 0.055 mol) was added dropwise during
~10 minutes to 15.2 g (0.046 mol) of freshly prepared HGeCl
3
•2(C
2
H
5
)
2
O. The reaction proceeded with liberation of heat. The reaction flask was immersed in a water bath at room temperature. The reaction mixture turned turbid upon addition of the first 3 mL of methyl acrylate and then clarified to a colorless solution. The reaction mixture was stirred overnight at room temperature and the excess ether and methyl acrylate were removed in a rotary evaporator. The milky white liquid product obtained was used for further reactions. Yield: 10.2 g (83%). NMR (CDCl
3
):
1
H; 2.29(t), 2.78(t), 3.74(s).
13
C; 28.6,
28.6, 53.1, 166.5
Cl
3
Ge(CH
2
)
2
COOH Acrylic acid (6.0 mL, 0.086 mol) was added dropwise to 2.6g
(0.069 mol) HGeCl
3
•2(C
2
H
5
)
2
O complex cooled to 0°C in an ice-water bath. The reaction mixture was stirred for ~12 hours. The excess ether and acrylic acid were removed by rotary evaporation. The residue was extracted with chloroform which was later removed in a rotary evaporator. Yield: 14.1 g (80%).
Cl
3
Ge(CH
2
)
2
CONH
2
Acrylamide (10.6 g, 0.15 mol) was added to 32.8 g (0.10 mol) of the HGeCl
3
•2(C
2
H
5
)
2
O complex cooled to 0°C in an ice-water bath. The reaction mixture was stirred for ~12 hours. After removal of excess ether and acrylamide the residue was washed twice with 30 mL portions of chloroform. Yield: 19.0 g (76%). NMR (D
2
O):
1
H;
0.96(t), 2.13(t).
13
C; 12.4, 26.2, 179.4
[GeW
11
O
39
Sn(CH
2
)
2
COOCH
3
] 5. A solution of Cl
3
Sn(CH
2
)
2
COOCH
3
(1.20 g, 3.85 mmol) in 30 mL DMF was treated with K
8
[GeW
11
O
39
] (4.31g, 1.34 mmol) and the

Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004 reaction mixture was stirred for ~3 hours. Since the reaction mixture remained turbid, 7 mL 0.5 M acetate buffer (pH 4.7) was added and the mixture was stirred overnight. Solid
CsCl (6 g) was added to the clear solution, followed by 90 mL ethanol. The white precipitate obtained was filtered off and washed with ethanol/water (v:v 1:1), ethanol, and ether. It was dried in a vacuum oven at ~80°C. Yield: 4.0 g (79%). Elemental analysis for Cs
5
[GeW
11
O
39
Sn(CH
2
)
2
COOCH
3
]: Found(calcd.), C, 1.32(1.33); H,
0.27(0.20).
Cs
6
[GaW
11
O
39
Sn(CH
2
)
2
COOCH
3
] was prepared analogously. Yield: 63%.
[SiW
11
O
39
Sn(CH
2
)
2
CN] 5Five milliliters of a DMF solution of Cl
3
Sn(CH
2
)
2
CN (with a concentration of 1.2 mmol/mL) were mixed with 45 mL DMSO. K
8
[SiW
11
O
39
] (4.0 g,
1.26 mmol) was added and the reaction mixture was stirred in a water bath at 90° C for 2 hours and afterwards was left stirring overnight at room temperature. Some unreacted starting material was removed by filtration. Twenty milliliters of a saturated aqueous solution of CsCl was added to the filtrate, followed by 120 mL ethanol. The white precipitate obtained was filtered off and recrystallized from the minimum amount of boiling water. The product was dried overnight in a vacuum oven at ~80°C. Yield: 3.4 g
(75%). Elemental analysis for Cs
5
[SiW
11
O
39
Sn(CH
2
)
2
CN]: Found(calcd.), C, 1.2(1.0); H,
0.13(0.11); N, 0.41(0.40).
[GaW
11
O
39
Sn(CH
2
)
2
CN] 6 .Three milliliters of a DMF solution of Cl
3
Sn(CH
2
)
2
CN with a concentration of 1.2 mmol/mL was mixed with 17 mL DMF and 20 mL H
2
O.
Following the addition of Na
9
[GaW
11
O
39
] (3.79 g, 1.24 mmol) the reaction mixture was stirred overnight at room temperature. Some insoluble residue was removed by filtration.
Solid CsCl was added to the filtrate until saturation (~8 g), followed by 80 mL ethanol.

Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
The white precipitate obtained was filtered off and recrystallized from a minimum amount of boiling water. The product was dried in a vacuum oven at ~80°C. Yield: 2.4 g
(50%). Elemental analysis for Cs
6
[GaW
11
O
39
Sn(CH
2
)
2
CN]: Found(calcd.), Cs,
21.2(20.6); Ga, 1.7(1.8); W, 52.5(52.3); Sn, 3.9(3.1); C, 0.93(0.93); H, 0.11(0.10); N,
0.36(0.36).
[SiW
11
O
39
Ge(CH
2
)
2
COOCH
3
] 5. A solution of Cl
3
Ge(CH
2
)
2
COOCH
3
(1.33 g, 5.0 mmol) in 50 mL DMF was treated with K
8
[SiW
11
O
39
] (6.45g, 2.0 mmol) and the resulting slurry was stirred for ~20 hours at room temperature. Unreacted [SiW
11
O
39
]
8was removed by filtration and the volume of the reaction mixture was reduced in a rotary evaporator to about 15 mL. A solution of 6.0 g of CsCl(s) in 10 mL of water was added to the reaction mixture. Unreacted Cl
3
Ge(CH
2
)
2
COOCH
3
, which separates as a white foam on the surface, was removed mechanically. The reaction mixture was refrigerated, but no precipitation was observed. The addition of 40 mL of cold ethanol (5°C) caused the immediate formation of a white precipitate which was filtered off and washed with ethanol/water (v:v 1:1), ethanol and ether. The product was dried overnight in a vacuum oven at ~80°C. Yield: 6.9 g (89%). Elemental analysis for
Cs
5
[SiW
11
O
39
Ge(CH
2
)
2
COOCH
3
]: Found(calcd.), Cs, 18.7(18.7); Si, 0.79(0.79); W,
56.6(56.9); Ge, 1.96(2.04); C, 1.31(1.35); H, 0.22(0.20).
[SiW
11
O
39
Ge(CH
2
)
2
COOH] 5 A solution of Cl
3
Ge(CH
2
)
2
COOH (0.78 g, 3.09 mmol) in
40 mL of DMF/H
2
O (v:v 1:1) was treated with K
8
[SiW
11
O
39
] (4.0 g, 1.24 mmol). The pH after complete addition of K
8
[SiW
11
O
39
] was 2.2. The reaction mixture was stirred for
~12 hours. Solid CsCl (~12 g) was added to the clear solution, which was stirred until complete dissolution. Since no precipitation was observed, 80 mL ethanol was added to

Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004 the reaction mixture and the white precipitate obtained was filtered off with suction. The product was recrystallized from a minimum amount of boiling water and dried overnight in a vacuum oven at ~80°C. Yield: 3.5 g (75%). Elemental analysis for
Cs
5
[SiW
11
O
39
Ge(CH
2
)
2
COOH]: Found(calcd.), C, 0.99 (0.99); H, 0.17(0.14).
[SiW
11
O
39
Ge(CH
2
)
2
CONH
2
] 5. A solution of Cl
3
Ge(CH
2
)
2
CONH
2
(0.68 g, 2.72 mmol) in 40 mL of DMF/H
2
O (v:v 1:1) was treated with K
8
[SiW
11
O
39
] (4.0 g, 1.24 mmol) and the mixture was stirred for ~20 hours. Solid CsCl (~12 g) was added, followed by 80 mL ethanol. The white precipitate obtained was filtered off and recrystallized from a minimum amount of boiling water. The first batch of recrystallized compound (1.6 g) precipitated once the filtrate cooled down to room temperature. A second batch (2.6 g) was obtained upon addition of 50 mL ethanol to the filtrate. Both fractions were dried overnight in a vacuum oven at ~80°C. Total yield: 4.2 g (88%).
[GaW
11
O
39
Ge(CH
2
)
2
COOH] 6. A solution of Cl
3
Ge(CH
2
)
2
COOH (0.78 g, 3.09 mmol) in 40 mL of DMF/H
2
O (v:v 1:1) was treated with K
9
[GaW
11
O
39
] (4.14 g, 1.24 mmol).
The pH after the complete addition of K
9
[GaW
11
O
39
] increased to 2.6. The reaction mixture was stirred for 12 hours. Solid CsCl (10 g) was added to the clear solution, which was stirred until complete dissolution of CsCl occurred. The solution turned slightly turbid. 80 mL ethanol was added and the white precipitate obtained was filtered off with suction. The product was recrystallized from a minimum amount of boiling water and dried overnight in a vacuum oven at ~80°C. Yield: 2.53 g (53%).
[GaW
11
O
39
Ge(CH
2
)
2
CONH
2
] 6. A solution of Cl
3
Ge(CH
2
)
2
CONH
2
(0.81 g, 3.23 mmol) in 40 mL DMF/H
2
O (v:v 1:1) was treated with Na
9
[GaW
11
O
39
](4.0 g, 1.31 mmol) was added. The pH after the complete addition of Na
9
[GaW
11
O
39
] increased to 2.5. The

Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004 reaction mixture was stirred for 15 hours and filtered . Solid CsCl (12 g), followed by 80 mL ethanol, was added and the white precipitate obtained was filtered off with suction.
The product was recrystallized from the minimum amount of boiling water. The white precipitate was filtered off and dried overnight in a vacuum oven at ~80°C. Yield: 3.15 g
(63%). Elemental analysis for Cs
6
[GaW
11
O
39
Ge(CH
2
)
2
CONH
2
]: Found(calcd.), C,
1.1(0.99); H, 0.17(0.17); N 0.39(0.38).